PL224424B1 - Method for modification of fabrics using reactive derivatives of cyclodextrins - Google Patents

Description

Description of the invention

The subject of the invention is a method of modifying fabrics with the aid of reactive cyclodextrin derivatives.

Cyclodextrins (CDs) are macrocyclic oligosaccharides, composed of 6-8 (or more) D-glucose residues linked together by 1-4 glycosidic bonds. The shape of the molecule is similar to a torus, the outer surface of which is more hydrophilic than the hydrophobic cavity. The most important feature of cyclodextrins is the ability to form inclusion complexes. They act as a host, while the guest molecule penetrates the cavity inside the oligosaccharide molecule without forming covalent bonds. Useful reviews on cyclodextrins include: (1) Szejtli J .: Cyclodextrins and Their Inclusion Complexes; Akademiai Kiado, Budapest, 1982, (2) Dodziuk H., Cyclodextrins and Their Complexes: Chemistry, Analytical Methods, Applications, Wiley-VCH; 2006.

The search for new materials that could meet the growing application requirements resulted in the interest in modifying natural fibers with cyclodextrins. In this way, the modified textiles can be used, among others for prolonged release of perfumes (e.g. in aromatherapy), encapsulation of odor-causing molecules (e.g. sweat - textiles for making socks and underwear, shoe insoles), controlled release of active substances (antibacterial, antifungal or insect repellent), protection and stabilization other chemicals that may be on the surface of the fabric.

Due to their specific properties, cyclodextrins have a number of potential applications in the textile industry. They can, among others constitute a new class of excipients. By forming complexes with detergent molecules, they can act as antifoams, which makes it possible to reduce the amount of water during washing. In addition, adding them to the rinse bath allows detergent residues to be bound. During the production and storage of washing powders, the amount of fragrances added to them is significantly reduced. By using cyclodextrins, stable complexes with the fragrance are obtained, which is released only in the presence of water.

The most common method of depositing cyclodextrins on the surface of the material is their chemical bonding through an intermediary molecule that is capable of reacting both with the cyclodextrin hydroxyl groups and with moieties present on the fiber surface of the modified material. This requires that the cyclodextrin molecules retain the ability to form inclusion complexes and, accordingly, be permanently bonded to the fiber surface (resistance to hydrolysis and elevated temperature during multiple washing / ironing cycles). Chemical compounds used as a link between the cyclodextrin molecule and the textile material should be non-toxic, non-allergenic, and additionally react quickly, under mild conditions and in an aqueous environment, with groups associated with the modified textile material.

In the literature, the most commonly used fasteners are: sodium 2,6-dichloro-4-hydroxy-1,3,5-triazole (MCT) [(3) Moldenhauer JP, Reuscher H., Textile finishing with MCT-cyclodextrin, Proceedings of the Ninth International Symposium on Cyclodextrins, Santiago de Compostela, 1998;

(4) Nostro P., Fratoni L., Baglioni P., J. Inclusion Phenom. Macrocyclic Chem., 2002, 44, 423], N-methylacrylamide (NMA) [(5) Nostro P., Fratoni L., Baglioni P., J. Inclusion Phenom. Macrocyclic Chem., 44, 423, 2002; (6) Lee M. H., Yoon K. J, Ko S. W., J. Appl. Polym. Sci., 78, 1986, 2000, (7) Lee M. H., Yoon K. J., Ko S. W., J. Appl. Polym. Sci. 80, 438, 2001], polycarboxylic acids (citric, butane tetracarboxylic and poly (acrylic)) [(8) US 7048769, 2006; (9) Martel B., Morcellet M., Ruffin D., Ducoroy L., Weltrowski M., J. Inclusion Phenom. Macrocyclic Chem., 44, 443, 2002], imidazolidone derivatives [(10) US 6861520], aliphatic and aromatic halogenoamines [(11) US patent application 2005 / 0080254A1] and halogenated heterocycles (m. including triazines, quinolines, pyrimidines) [(12) US 5,728,823].

MCT-CD (Monochlorotriazinyl-3-cyclodextrin) is currently the only commercially produced and commercially available cyclodextrin derivative that effectively binds to natural and some artificial fibers. It has been tested for toxicity according to OECD guidelines and approved for use [(13) Buschmann H. J, Knittel D., Schollmeyer E., J. Inclusion Phenom. Macrocyclic Chem., 2001, 40, 169].

PL 224 424 B1

The citric acid (CTR) method consists in soaking the fabric in a bath containing CTR, CD and catalyst (eg Na ₂ HPO ₄ ), drying and then heating at 170-190 ° C for a few minutes. After the heat treatment, the fabric is rinsed and dried. This method is widely described in the literature [(14) Martel B., Morcellet M., Ruffin D., Ducoroy L., Weltrowski M., J. Inclusion Phenom. Macrocyclic Chem., 44, 443, 2002; (15) Martel, B., Weltrowski, M., Ruffin, D., Morcellet, M., J. Appl. Polym. Sci. 83, 1449, 2002; (16) Ducoroy, L .; Martel, B .; Bacquet, M .; Morcellet, MJ Appl. Polym. Sci., 103, 3730, 2007, (17) Ducoroy, L .; Bacquet, M .; Martel, B .; Morcellet, M. React. Funct. Polym., 68, 594, 2008].

Fibrous materials with chemically bound cyclodextrins have sorption properties, which can also be used, among others, in as cigarette filters and for water purification, they are described in US patent (18) US 4357468. The contained substances can be recovered quantitatively from such material.

Cyclodextrins can also be used when dyeing textiles. The literature describes the possibility of dyeing polyamide, polyester and cotton fibers with this method. Patent application (19) WO 9850511 describes a method using cyclodextrins and their derivatives to protect dyed textiles during their washing and rinsing.

Another area of application of cyclodextrins and their derivatives is the use in textile finishing processes, as described in the German patent (20) DE 4035378. Physically attached cyclodextrin molecules, forming complexes with sweat molecules or its degradation products, prevent their penetration into the textile material - see German patent description (21) DE 10101294.

The attachment of cyclodextrins to the textile material makes it possible to obtain new textile materials with unprecedented properties. The search for such materials is in line with the current trend in the development of research on materials that can meet the constantly growing customer requirements for clothing and footwear.

Unexpectedly, it turned out that carrying out the reaction of fabric modification by successively: etherification with dichloroalkanes, condensation with diamines and condensation with a reactive tosyl derivative of cyclodextrins, leads to the formation of fabrics containing chemically bound cyclodextrins, with the possibility of practical use as a carrier for chemical species incorporated in the cavities of cyclodextrins. Examples of such species are fragrances which, when released, impart a fresh smell to fabrics, bactericides, bacteriostatic agents, and fungus and obliterans used to protect fabrics from degradation by bacteria and fungi.

The essence of the invention is a method of fabric modification with the use of reactive cyclodextrin derivatives, comprising the initial preparation of the fabric and then attaching a reactive cyclodextrin derivative to the fabric, which consists of the following steps:

A. Obtaining chlorinated cellulose by etherification of cellulose with dichloroalkane in alkaline environment,

B. Conversion of the chlorine derivative cellulose obtained in stage A into an amine derivative of cellulose by means of diamine,

C. Substitution of the α-, β-, γ-cyclodextrin tosyl group by primary groups of the amine derivative of cellulose, formed in step B.

Preferably the chlorine derivative of cellulose is obtained by etherification of cellulose with dichloroethane.

Preferably, the conversion of the chlorinated cellulose obtained in step A into the amine derivative is carried out with hexamethylenediamine.

Preferably in step C a tosyl derivative of β-cyclodextrin is used.

The fabric modified with the reactive cyclodextrin derivatives according to the invention can be used to incorporate aromatic, bactericidal, bacteriostatic, fungicidal and fungistatic substances into the textile material in order to release them gradually.

An additional advantage of the fabrics modified in this way is the possibility of absorption of sweat components by unfilled cavities of cyclodextrin molecules.

The following is a diagram of the reactions taking place during the modification of fabrics with the reactive cyclodextrin derivatives according to the invention.

PL 224 424 B1

AGU is the cellulose anhydroglucose unit and Ts is the tosyl group.

The cyclodextrin reactive derivative used to introduce cyclodextrins onto fabrics is preferably 6- ^? -P-toluenesulfonyl-3-cyclodextrin. This derivative is obtained by the reaction shown in the scheme below and described in the literature (22) Brady B., Lynam N., O'Sullivan T., Ahern C., Darcy R., Organic Syntheses, Coll. Vol. 10, p. 686, Vol. 77, p. 220, 2004:

The subject matter of the invention is illustrated in detail in the following non-limiting examples.

Example 1

Approximately 100 g of fabric (cotton fabric, 1x1 plain weave, two-ply, basis weight 106 g / m - T) was placed in a 3L conical flask, 1.5L of 20% NaOH aqueous solution was added, placed on a laboratory shaker and shaken at room temperature for Thirty minutes. At this time, excess NaOH solution was poured off. The fabric T was gently squeezed out. The wet T-fabrics were placed back in the flasks and 0.6L of distilled water and 0.2L were added

1,2-dichloroethane. The flasks were then shaken on a laboratory shaker for 1 hour at room temperature. After this time, the solution was poured into a pear separator to separate the organic layer. The fabric T was imprinted. Rinsed several times in distilled water while monitoring the pH with a universal indicator. Finally, the fabric T was squeezed out firmly and then placed in the conical flask. 0.6L of 1,4-dioxane, 60 g of hexamethylenediamine and 20 g of tosyl cyclodextrin (TsCD) were added and then shaken on a laboratory shaker at maximum speed for 1 hour. After this time, the fabrics T were rinsed several times in distilled water and allowed to dry completely at room temperature.

E xample 2

About 100 g of fabric (cotton fabric, linen weave 1x1, two-layer, weight ₂

141 g / m - 2T) was placed in a 3L conical flask, 1.5L of 20% NaOH aqueous solution was added, placed on a laboratory shaker and shaken at room temperature for 30 minutes. At this time, excess NaOH solution was poured off. The 2T fabric was gently squeezed. The wet 2T fabrics were placed back in the flasks and 0.6L of distilled water and 0.2L were added

1,2-dichloroethane. The flasks were then shaken on a laboratory shaker for 1 hour at room temperature. After this time, the solution was poured into a pear separator to separate the organic layer. The 2T fabric was impressed. Rinsed several times in distilled water while monitoring the pH

PL 224 424 B1 by means of a universal indicator. Finally, the 2T fabric was squeezed out tightly and then placed in a conical flask. 0.6L of 1,4-dioxane, 60 g of hexamethylenediamine and 20 g of tosyl cyclodextrin (TsCD) were added and then shaken on a laboratory shaker at maximum speed for 1 hour. After this time, the 2T fabric was rinsed several times in distilled water and allowed to dry completely at room temperature.

Example 3

About 100 g of fabric (cotton fabric, brushed with 1x1 plain weave, basis weight 151 g / m - F) was placed in a 3L conical flask, 1.5L of 20% NaOH aqueous solution was added, placed on a laboratory shaker and shaken at room temperature for Thirty minutes. At this time, excess NaOH solution was poured off. Fabric F was gently squeezed. The wet F fabrics were placed back in the flasks and 0.6L of distilled water and 0.2L were added

1,2-dichloroethane. The flasks were then shaken on a laboratory shaker for 1 hour at room temperature. After this time, the solution was poured into a pear separator to separate the organic layer. Fabric F was impressed. Rinsed several times in distilled water while monitoring the pH with a universal indicator. Finally, the fabric F was squeezed out firmly and then placed in the conical flask. 0.6L of 1,4-dioxane, 60 g of hexamethylenediamine and 20 g of tosyl cyclodextrin (TsCD) were added and then shaken on a laboratory shaker at maximum speed for 1 hour. After this time, the fabrics F were rinsed several times in distilled water and allowed to dry completely at room temperature.

Example 4

About 100 g of fabric (cotton fabric with a loose linen weave 1x1, grammage ₂ g / m - C) was placed in a 3L conical flask, 1.5L of a 20% NaOH aqueous solution was added, placed on a laboratory shaker and shaken at room temperature for 30 minutes. minutes. At this time, excess NaOH solution was poured off. Cloth C was gently squeezed. The wet C cloths were placed back in the flasks and 0.6L of distilled water and 0.2L were added

1,2-dichloroethane. The flasks were then shaken on a laboratory shaker for 1 hour at room temperature. After this time, the solution was poured into a pear separator to separate the organic layer. The C fabric was blotted and rinsed several times in distilled water while monitoring the pH with the universal indicator. Finally, the fabric C was squeezed tightly and placed in the conical flask. 0.6L of 1,4-dioxane, 60 g of hexamethylenediamine and 20 g of tosyl cyclodextrin (TsCD) were added and then shaken on a laboratory shaker at maximum speed for 1 hour. After this time, the fabric was rinsed several times in distilled water and allowed to dry completely at room temperature.

E xample 5

Study of weight gain of fabrics subjected to Ts-CD modification

The weight gain tests of the Ts-CD modified fabrics produced in Examples 1 to 4 were carried out by the weight method.

The test results are presented in Table 1.

T a b e l a 1

Mass increase of fabrics subjected to Ts-CD modification

Fabric modification according to the invention (Designation of a fabric sample) Am [g] Percentage of weight gain [%] Example 1 (T) 0.26 2.20 Example 2 (2T) 0.25 2.30 Example 3 (F) 0.11 0.99 Example 4 (C) 0.07 0.60

Example 6

Testing nitrogen content in samples of Ts-CD modified fabrics

Tests for nitrogen content in the samples of Ts-CD modified fabrics, produced in Examples 1 to 4, were carried out by the Kiejdhal method with final titration determination.

PL 224 424 B1

The analyzed sample was mineralized in concentrated sulfuric acid with the addition of selenium as a catalyst, hydrogen peroxide as an oxidant and potassium sulphate to increase the boiling point of sulfuric acid. After mineralization of the sample, the nitrogen contained in it appears in the form of acid ammonium sulphate. The cooled solution was treated with a strong base solution (NaOH) and the liberated ammonia was distilled with steam into a saturated boric acid solution with the addition of a Tashiro indicator. The solution of ammonia in boric acid was determined by titration with standard hydrochloric acid solution (0.01 M until the initial color was obtained, as before the ammonia absorption).

The test results are presented in Table 2.

T a b e l a 2

Percentage of nitrogen content in TsCD modified fabrics

Fabric modification according to the invention (Designation of a fabric sample) Sample weight [g] % N Example 1 (T) 2.6921 0.086 Example 2 (2T) 3.6036 0.140 Example 3 (F) 2.5163 0.305 Example 4 (C) 2.0416 0.178

Based on the results of the analyzes shown in examples 5 and 6, we can unequivocally state that the modification carried out resulted in the introduction of cotton cyclodextrin derivatives into various types of fabrics, which can be a carrier for fragrances that give fabrics a fresh smell, as well as bactericidal, bacteriostatic, fungicidal and fungistatic substances in to protect fabrics against degradation caused by bacteria and fungi.

Literatura (1) Szejtli J .: Cyclodextrins and Their Inclusion Complexes, Akademiai Kiado, Budapest, 1982.

(2) Dodziuk H., Cyclodextrins and Their Complexes: Chemistry, Analytical Methods, Applications, Wiley-VCH; 2006.

(3) Moldenhauer J.P., Reuscher H., Textile finishing with MCT-cyclodextrin, Proceedings of the Ninth International Symposium on Cyclodextrins, Santiago de Compostela, 1998.

(4) Nostro P., Fratoni L., Baglioni R, J. Inclusion Phenom. Macrocyclic Chem., 2002, 44, 42.

(5) Nostro P., Fratoni L., Baglioni R, J. Inclusion Phenom. Macrocyclic Chem., 44, 423, 2002.

(6) Lee M.H., Yoon K.J., Ko S.W., J. Appl. Polym. Sci., 78, 1986, 2000.

(7) Lee M.H., Yoon K.J., Ko S.W., J. Appl. Polym. Sci. 80,438,2001.

(8) US 7048769, 2006.

(9) Martel B., Morcellet M., Ruffin D., Ducoroy L., Weltrowski M., J. Inclusion Phenom. Macrocyclic Chem., 44, 443, 2002.

(10) U.S. Patent 6861520.

(11) Report. stalemate. US 2005 / 0080254A1.

(12) U.S. Patent 5,728,823.

(13) Buschmann H.J, Knittel D., Schollmeyer E., J. Inclusion Phenom. Macrocyclic Chem., 2001, 40, 169.

(14) Martel B., Morcellet M., Ruffin D., Ducoroy L., Weltrowski M., J. Inclusion Phenom. Macrocyclic Chem., 44, 443, 2002.

(15) Martel, B., Weltrowski, M., Ruffin, D., Morcellet, M., J. Appl. Polym. Sci. 83, 1449, 2002.

(16) Ducoroy, L .; Martel, B .; Bacquet, M .; Morcellet, M. J. Appl. Polym. Sci., 103, 3730, 2007.

(17) Ducoroy, L .; Bacquet, M .; Martel, B .; Morcellet, M. React. Funct. Polym., 68, 594, 2008].

(18) US Patent 4357468 (19) Patent WO 9850511 (20) Patent DE 4035378.

(21) Patent DE 10101294 (22) Brady B., Lynam N., O'Sullivan T., Ahem C., Darcy R., Organic Syntheses, Coll. Vol. 10,

Claims (4)

Patent claims A method of modifying fabrics with reactive cyclodextrin derivatives, comprising pretreating the fabric and then attaching to the fabric a reactive cyclodextrin derivative, comprising the following steps: A. Preparation of chlorinated cellulose by etherification of cellulose with dichloroalkane in alkaline environment; B. Conversion of the chlorine derivative cellulose obtained in step A into an amine derivative of cellulose by means of diamine; C. Substitution of the α-, β-, γ-cyclodextrin tosyl group by primary groups of the amine derivative of cellulose, formed in step B. 2. The method according to p. A process as claimed in claim 1, characterized in that the chlorine derivative cellulose is obtained by etherification of cellulose with dichloroethane. 3. The method according to p. A process as claimed in claim 1, characterized in that the conversion of the chlorine derivative cellulose obtained in step A into the amine derivative is carried out with hexamethylenediamine. 4. The method according to p. The process of claim 1, wherein the tosyl derivative of β-cyclodextrin is used in step C.